IL33907A - Process for the production of cyclohexanedione-(1,2)-hemihydrate - Google Patents
Process for the production of cyclohexanedione-(1,2)-hemihydrateInfo
- Publication number
- IL33907A IL33907A IL33907A IL3390770A IL33907A IL 33907 A IL33907 A IL 33907A IL 33907 A IL33907 A IL 33907A IL 3390770 A IL3390770 A IL 3390770A IL 33907 A IL33907 A IL 33907A
- Authority
- IL
- Israel
- Prior art keywords
- process according
- nitric acid
- cyclohexanol
- reaction
- hemihydrate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 239000011133 lead Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000659 freezing mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Process for the production of hexaned BAYER AR The present invention relates to a process for the production of It is known that the oxidation of cyclohexanol with lute nitric acid at temperatures of around leads to adipic This reaction has for a long time been used in industry for the manufacture of adipic It is also known that the oxidation takes a different course at temperatures up to about and at higher nitric acid A pound which is interpreted by most authors as a tetracyclic hemihydrate of is produced in moderate yields 78 page Anteunis and Verzele pages in their work on the manufacture of use the above mentioned literature references and give instructions for the production of the hemihydrate of which they call They state that their compound is identical with that described in but interpret it as 2 2 If their instructions are followed it is necessary to employ extreme especially if 7 strength nitric acid it is used because of the somewhat higher Even as the process is carried out with small the reaction given inadequate easily get out of control because of its strongly exothermic character and take place When the reaction takes place normally in accordance with the the hemihydrate is obtained mixed with considerable amounts of lie acid of formula This compound tends to undergo a strongly exothermic is not suitable economical manufacture and above all for manufacture which is safe against as also emerges from the following comments in the working in this way the tendency of the reaction to get cut of control and to become nearly explosively exothermic is also increased and the necessary care and precautions are to be The hitherto obtainable yield of at most is achieved by means of reaction conditions i which the reaction easily becomes uncontrollable and can take an explosive so that manufacture on a larger scale is Since the product hitherto obtainable according to the above mentioned process proves on titration with hydroxylamine hydrochloride at using sodium hydroxide solution as is the usual procedure in the determination of ketones only to contain about 80 of the data on yield given above of have to be correspondingly It has now been found that can be manufactured with less danger and in good even on a larger The present invention provides a process for the production of hydrate which comprises introducing hydrous cyclohexanol and nitric acid simultaneously into nitric acid containing a catalytic amount of nitrous acid with thorough mixing at a temperature of to the concentration of the nitric acid being maintained at at least by the crude which or which is caused to is isolated and washed with It is essential to use hydrous that cyclohexanol containing at room Of course it is also possible to use amounts of provided it is made sure that these suffice to prevent of the cyclohexanol point in the initially introduced nitric acid in the temperature range of In about moles of nitric acid are used per mole of hydrous This is preferably done by providing about of aqueous per cent by weight nitric acid and adding about moles of a concentrated per cent by weight nitric acid in the course of the reaction in aliquot parts simultaneously with the hydrous Most the process involves the use of a total of at least about 3 moles of nitric acid per mole of It is very important for the safe operation of the process to avoid an accumulation of the reactant3 in the foam which may which achieved by introduction of the reactants below the It is important the smooth start of the reaction that the reaction mixture should contain at least catalytic amounts of nitrous It will sometimes suffice to employ nitric acid which is coloured brown by nitrous or to introduce nitrous gases or nitro3ylsulphuric acid to 1 g preferably to g per mole into the nitric acid In order to be on the safe it is however able to add to the reaction mixture about 200 mg of alkali preferably sodium per mole of A further increase in the yield can be achieved if the reaction is carried out in the presence of catalytic amounts of a heavy metal salt example a sulphate a of gold or lead Here amounts of about g of for example per mole of cyclohexanol are The reaction is carried out in the temperature range of preferably about at about it being necessary to ensure intensive mixing of the reaction The course of the reaction can optionally also be followed by measuring the amounts of gas about litres of gas constituent being evolved per mole of cyclohexanol after saturation of the reaction The mixtures may be worked up in the temperature range specified for carrying out the preferably at about by suction any small amounts of nitrolic acid formed at the same time which may remain in the filter cake can be removed in a simple manner by eluting with warm water temperature preferably about To destroy the nitrolic acid accumulated in the mother it is expedient to heat the mother liquor in small portions to about in a continuous flow The resulting solution then contains residual nitric adipic acid which forms from the nitrolic acid through almcs quantitative If a plant for the production of adipic acid is the solution formed can therefore be fed into the plant at a suitable The process according to the invention can be carried out both continuously and The obtained is an intermediate for the production of plant protection The process of the present invention is illustrated by the following are placed in a flask provided with 2 dropping gas delivery tube and The ends of the dropping funnels are below the surface of the initial which is cooled by a freezing mixture to and g sodium nitrite is In the course of about 3 there are taneously added drppwise cc cyclohexanol with a water content of about 10 per cent by volume and 102 cc of nitric In the first minutes the temperature is allowed to rise from to about After completion of the wise stirring is continued for about 2 hours at suction filtration is then effected on a glass suction 200 cc of water are added to the filter cake which is then heated to with filtered off with suction after cooling to room washed with 50 cc of cold sharply filtered off with suction and dried overnight on After final drying at reduced pressure and about g are Yield with reference to dried of the Yield with reference to hemihydrate content of the If this experiment is repeated as described in the is dropwise to the total amount of nitric acid used strength 5 by weight the is only obtained in Example 2 If the procedure according to Example 1 is followed and silver nitrate is added to the initial nitric the following yields of are insufficientOCRQuality
Claims (10)
1. What we claim is: 1. A process for the production of cyclohexanedione-(l,2) hemihydrate which comprises introducing hydrous cyclohexanol and nitric acid simultaneously into nitric acid containing a catalytic amount of nitrous acid with thorough mixing at a temperature of 0° to 18°C, the concentration of the nitric acid "being maintained at at least 30% by weight.
2. A process according to claim 1 in which the cyclohexane-dione-(l,2) hemihydrate separating out from the reaction mixture is isolated then washed with water,
3. A process according to claim 1 or 2 in which the cyclohexanol is saturated with water.
4. A process according to claim 1 or 2 in which the cyclohexanol contains up to about 10% by weight of water.
5. A process according to any of claims 1-4 in which the total amount of nitric acid used is 2.5 moles per mole of hydrous cyclohexanol.
6. A process according to claim 5 in which the introduced nitric acid is added in an amount of 1 to 2 moles per mde of hydrous cyclohexanol.
7. A process according to claim 6 in ich the introduced nitric acid has a concentration of 60 to 100% by weight.
8. A process according to any of claims 5-7 in which the nitric acid into which the reactants are introduced is, provided in an amount of 1-3 moles per mole of hydrous cyclohexanol.
9. A process according to claim 8 in which the nitric acid into wHch the reactants are introduced has a concentration of 30 to 60% by weight.
10. A process according to any of claims 1 to 9 in which the cyclohexanol and nitric acid are introduced into the nitric acid below the surface thereof. 12. A process according to any of claims 1 to 11 in which the reaction medium contains a catalytic amount of a heavy metal salt. 13. A process according to claim 12 in which the reaction medium contains 0.1 to 1.0 g of a sulphate or nitrate of copper, gold, lead or silver, per mole of cyclohexanol. 14. A process according to claim 13 in which the reaction medium contains 0.1 to 1.0 g of silver nitrate per mole of cyclohexanol. 15. A process according to any of claims 1 to 14 in which the reaction is effected at 5° to 15°C. 16. A process according to claim 15 in •vti.ch the reaction is effected at about 10°C. 17. A process acoording to any of claims 1-16 in which the course of the reaction is followed by measuring the amount of gas evolved, according to any of claims 7 and 9 to 12, 18. A process/ for the production of cyclohexanedione-(l,2 ) hemihydrate substantially as hereinbefore described in any of the Examples. 19. A process according to any of claims 1 to 18 when carried out in a continuous manner. 20. Cyclohexanediohe-(l,2) hemihydrate whenever prepared by a process according to any of claims 1 to 19.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691908676 DE1908676C3 (en) | 1969-02-21 | Process for the preparation of cyclohexanedione-U ^ hemihydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL33907A0 IL33907A0 (en) | 1970-04-20 |
| IL33907A true IL33907A (en) | 1973-02-28 |
Family
ID=5725887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL33907A IL33907A (en) | 1969-02-21 | 1970-02-16 | Process for the production of cyclohexanedione-(1,2)-hemihydrate |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS4941194B1 (en) |
| BE (1) | BE746297A (en) |
| BR (1) | BR7016913D0 (en) |
| CH (1) | CH529084A (en) |
| CS (1) | CS161105B2 (en) |
| FR (1) | FR2032942A5 (en) |
| GB (1) | GB1279192A (en) |
| IL (1) | IL33907A (en) |
| NL (1) | NL7002288A (en) |
| RO (1) | RO56199A (en) |
-
1970
- 1970-02-12 CH CH206370A patent/CH529084A/en not_active IP Right Cessation
- 1970-02-16 IL IL33907A patent/IL33907A/en unknown
- 1970-02-18 NL NL7002288A patent/NL7002288A/xx unknown
- 1970-02-18 GB GB7795/70A patent/GB1279192A/en not_active Expired
- 1970-02-19 RO RO62509A patent/RO56199A/ro unknown
- 1970-02-19 JP JP45013897A patent/JPS4941194B1/ja active Pending
- 1970-02-20 BE BE746297D patent/BE746297A/en unknown
- 1970-02-20 FR FR7006217A patent/FR2032942A5/fr not_active Expired
- 1970-02-20 BR BR216913/70A patent/BR7016913D0/en unknown
- 1970-02-23 CS CS1208A patent/CS161105B2/cs unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7002288A (en) | 1970-08-25 |
| BR7016913D0 (en) | 1973-04-12 |
| IL33907A0 (en) | 1970-04-20 |
| DE1908676A1 (en) | 1970-09-03 |
| RO56199A (en) | 1974-03-01 |
| GB1279192A (en) | 1972-06-28 |
| CS161105B2 (en) | 1975-05-04 |
| DE1908676B2 (en) | 1977-04-28 |
| JPS4941194B1 (en) | 1974-11-07 |
| CH529084A (en) | 1972-10-15 |
| FR2032942A5 (en) | 1970-11-27 |
| BE746297A (en) | 1970-08-20 |
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